Source/drain performance through conformal solid state doping

ABSTRACT

A method for improving source/drain performance through conformal solid state doping and its resulting device are disclosed. Specifically, the doping takes place through an atomic layer deposition of a dopant layer. Embodiments of the invention may allow for an increased doping layer, improved conformality, and reduced defect formation, in comparison to alternate doping methods, such as ion implantation or epitaxial doping.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No. 15/144,481, filed on May 2, 2016, entitled “SOURCE/DRAIN PERFORMANCE THROUGH CONFORMAL SOLID STATE DOPING,” which is related to U.S. patent application Ser. No. 13/504,079, filed on Sep. 17, 2012, entitled “SYNTHESIS AND USE OF PRECURSORS FOR ALD OF GROUP VA ELEMENT CONTAINING THIN FILMS,” and issued as U.S. Pat. No. 9,315,896, the disclosures of which are hereby incorporated by reference in their entirety.

FIELD OF INVENTION

The present disclosure generally relates to processes for manufacturing electronic devices. More particularly, the disclosure relates to forming source/drain devices for NMOS and CMOS applications. Specifically, the disclosure discloses methods to improve a source/drain doping level with a conformal solid state doping technique.

BACKGROUND OF THE DISCLOSURE

Germanium has been considered as an appropriate material for use in CMOS and NMOS devices. With the trend towards smaller devices, contact area on the devices has become smaller, with a substantial increase in contact resistance. The increase in contact resistance has been countered with high source/drain doping.

The minimum contact resistivity on n-type Germanium has been achieved through antimony (Sb) ion implantation combined with laser annealing, according to Miyoshi et al., VLSI 2014, P180. However, the ion implantation process can be challenging for FinFET and nanowire devices.

As a result, a method for improving the source/drain performance is desired.

SUMMARY OF THE DISCLOSURE

In at least one embodiment in accordance with the invention, a method of forming a semiconductor device for source/drain applications is disclosed. The method comprises: providing a substrate for processing in a reaction chamber, the substrate having at least one formed source/drain region; performing a surface cleaning on the substrate, the surface cleaning removing oxides or native oxides from the substrate; performing an atomic layer deposition of a dopant layer on the substrate; performing an atomic layer deposition of a capping layer on the dopant layer; and performing a drive-in anneal step—e.g., to diffuse dopant from the dopant layer into the at least one formed source/drain region. The dopant layer can form a channel material for NMOS and CMOS devices.

In at least one embodiment in accordance with the invention, a method of forming a semiconductor device for source/drain applications is disclosed. The method comprises: providing a substrate for processing in a reaction chamber, the substrate having at least one formed source/drain region; performing a surface cleaning on the substrate; performing an atomic layer deposition of a dopant layer on the substrate; and performing an atomic layer deposition of a capping layer on the dopant layer. The dopant layer can form a channel material for NMOS and CMOS devices.

For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described herein above. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein without necessarily achieving other objects or advantages as may be taught or suggested herein.

All of these embodiments are intended to be within the scope of the invention herein disclosed. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments having reference to the attached figures, the invention not being limited to any particular embodiment(s) disclosed.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

These and other features, aspects, and advantages of the invention disclosed herein are described below with reference to the drawings of certain embodiments, which are intended to illustrate and not to limit the invention.

FIG. 1 is a flowchart of a method in accordance with at least one embodiment of the invention.

FIG. 2 is a flowchart of another method in accordance with at least one embodiment of the invention.

FIGS. 3A, 3B and 3C are illustrations of devices in accordance with embodiments of the invention.

It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of illustrated embodiments of the present disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and/or uses of the invention and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the invention disclosed should not be limited by the particular disclosed embodiments described below.

Atomic layer deposition (ALD) solid state doping (SSD) may be one way to form NMOS and CMOS devices. One reason for this may be the ability of ALD SSD to form films with excellent conformality and defect free features. Alternate doping methods, such as ion implantation, may introduce defects that ALD SSD can avoid during conformal doping of 3-D structures. ALD SSD also may provide the capability to deposit thin films with precise sub-nanometer thickness control, which thus determines the dose or number of atoms available at the surface to incorporate into the semiconductor as active dopant species. Embodiments in accordance with this invention may result in an increase of a doping level near an interface with an ultra-shallow doping profile. For example, a doping level greater than 1×10²⁰/cm³ with a diffusion depth less than 30 nm may be preferred.

In accordance with at least one embodiment of the invention, targets for the doping level through ALD SSD may approximately be 5×10²⁰/cm³. The ALD SSD doping level may be an order of magnitude greater than that achieved through an alternate method, such as epitaxial doping, of 5×10¹⁹/cm³. In addition, the alternate methods, such as ion implantation or epitaxial doping, may result in the morphology degradation of the film when incorporating high concentrations of substitutional or interstitial dopant species into the semiconductor matrix, and render the film inapplicable for its intended use in CMOS or NMOS devices.

FIG. 1 illustrates a method 100 in accordance with at least one embodiment of the invention. The method 100 may take place in a Pulsar® XP ALD reactor provided by ASM International B.V., for example.

The method 100 may include a first step 110 of source/drain (S/D) formation. The first step 110 may entail providing to a reaction chamber a substrate with a source/drain (S/D) regions formed within therein or thereon. For example, the substrate may comprise germanium, silicon, silicon germanium, or other III-V materials, having source and drain regions formed therein or thereon.

The method 100 may include a second step 120 of surface cleaning. The second step 120 may include a cleaning of a wafer with a cleaning agent. The effect of the second step 120 may be to remove any oxides or native oxides on the surface of the substrate. The presence of oxides or native oxides may degrade performance as it will adversely affect the contact resistivity of the substrate device.

In the second step 120, for example, a pretreatment may occur, such as a germanium wafer being cleaned with hydrofluoric acid (HF). Other potential cleaning agents include hydrochloric acid (HCl) or NF₃ plasma, for example. In accordance with at least one embodiment of the invention, the second step 120 may comprise a standard wet clean that may take place in a Horizon module provided by ASM International B.V., for example.

The method 100 may include a third step 130 of a dopant layer ALD. The dopant layer deposited in the third step 130 may include antimony, boron, arsenic, phosphorus, magnesium, carbon, silicon, or sulfur, for example. The dopant layer deposited in the third step 130 may be elemental or compound material. The third step 130 may take place at a temperature ranging between 20° C. and 450° C. The pressure in a reaction chamber, for this and other deposition steps described herein, is typically from about 0.01 to about 20 mbar, more preferably from about 1 to about 10 mbar. However, in some cases the pressure will be higher or lower than this range, as can be determined by the skilled artisan given the particular circumstances. The third step 130 may be repeated until a desired thickness is achieved, such as 0.1 nm to 15 nm. The dopant layer may include antimony or arsenic deposited in accordance with the disclosures of U.S. patent application Ser. No. 13/504,079, which is hereby incorporated by reference.

In accordance with at least one embodiment of the invention, a deposition of antimony may take place in the reaction chamber during the third step 130. The temperature of the reaction chamber during the third step 130 may range between 60-120° C., preferably between 60-100° C., and more preferably between 60-80° C. The third step 130 may be repeated as needed in order to obtain a desired thickness for the antimony layer, which in some instances may be 0.5 nm and 10 nm in other instances. In some embodiments, the third step 130 may not form a layer; instead, what may be formed may be isolated locations of material or islands, possibly separate or partially connected, of material comprising antimony.

In order to deposit antimony, the third step 130 may include the pulsing of a first precursor comprising a metal halide, such as SbCl₃, SbF₃, SbBr₃, or SbI₃, for example. The pulsing of the first precursor may range in duration between 0.1 and 5 seconds, and preferably between 0.5 and 2 seconds. The third step 130 may then include purging of the first precursor with a purge gas, such as N₂, Ar, or other inert gas. The pulsing of purge gas may range in duration between 5 and 15 seconds, and preferably between 5 and 10 seconds.

In order to deposit antimony, the third step 130 may include the pulsing of a second precursor comprising antimony. The second precursor may comprise at least one of: trimethyl silyl antimony, triethyl silyl antimony, antimony alkoxides, or antimony amides, for example. The second precursor may also comprise antimony bound to silicon atoms having a general formula of Sb(AR¹R²R³)₃, where A is Si or Ge and R¹, R², and R³ are alkyl groups comprising one or more carbon atoms. The pulsing of the second precursor may range in duration between 0.1 and 5 seconds, and preferably between 0.5 and 2 seconds. The third step 130 may then include purging of the second precursor with a purge gas, such as N₂, Ar, or other inert gas. The pulsing of purge gas may range in duration between 5 and 15 seconds, and preferably between 5 and 10 seconds.

The method 100 may include a fourth step 140 of a capping layer ALD. The layer deposited in the fourth step 140 may include silicon dioxide (SiO₂), silicon nitride (SiN), aluminum nitride (AlN), titanium nitride (TiN), silicon-containing carbon, or aluminum oxide (Al₂O₃), for example. The fourth step 140 may take place at a temperature ranging between 20° C. and 450° C. The capping layer deposition may not result in oxidation of the dopant layer formed in the third step 130.

For example, to form a layer of silicon dioxide, the fourth step 140 may include the pulsing of a first precursor comprising at least one of silane, disilane, trisilane, amino silane, or amino disilane, for example. The pulsing of the first precursor may range in duration between 0.1 and 5 seconds, and preferably between 0.5 and 2 seconds. The fourth step 140 may also include purging of the first precursor using a purge gas, such as N₂, Ar, or other inert gas. The pulsing of the purge gas may range in duration between 0.1 and 30 seconds, and preferably between 0.3 and 3 seconds.

The fourth step 140 may also include the pulsing of a second precursor comprising at least one of oxygen (O₂) plasma, ozone (O₃), water (H₂O), oxygen (O₂), hydrogen peroxide (H₂O₂), or other oxygen precursor. The pulsing of the second precursor may range in duration between 0.1 and 5 seconds, and preferably between 0.5 and 2 seconds. The fourth step 140 may then include a subsequent purging of the second precursor using the purge gas. The pulsing of the purge gas may range in duration between 0.01 and 15 seconds, and preferably between 0.05 and 2 seconds. Similar to the third step 130, the fourth step 140 may be repeated as necessary in order to form a layer having a desired thickness. In some instances, a bi-layer structure may be used for the fourth step 140, for example, a SiN/SiO₂ structure.

The method 100 may include a fifth step 150 of a drive-in anneal, which may be used to drive a dopant from the dopant ALD layer into the source and/or drain regions. During this step, the substrate may be subjected to a temperature range between 450° C. and 1100° C., resulting in improved dopant drive-in. The annealing may have a duration ranging between 1 second and 30 minutes.

The annealing in the fifth step 150 may play an important role in an overall thermal budget of the method 100. The overall thermal budget may determine a dopant diffusion depth of 30 nm, for example.

One issue solved by steps in accordance with the invention may be a solubility of the dopant. For example, there have been issues with low n-type dopant solubility in germanium. The third step 130 may allow for appropriate doping due to its improved conformality as well as its ability to limit the formation of defects due to ion implantation. With a drive-in anneal, deposition of a solid state dopant by ALD may allow for conformal 3-D doping of interfaces, which may not be possible in ion implantation. In addition, the defect formation resulting from other doping techniques may be avoided by ALD SSD.

The method 100 may include an optional sixth step 160 of a cap layer removal. The cap layer removal may be accomplished with an etching step, using hydrofluoric acid (HF), for example, as an etching agent.

In some instances, the cap layer removal may not be required. A drive-in anneal may obviate the need for the removal of the cap layer, if, for example, a conventional contact metal stack of Ti/TiN can serve as a cap layer to prevent dopant out diffusion.

FIG. 2 illustrates a method 200 in accordance with at least one embodiment of the invention. The method 200 may include a first step 210 of source/drain (S/D) formation. The first step 210 may entail providing to a reaction chamber a substrate with a source/drain (S/D) formed within or on the substrate. For example, the substrate may comprise germanium, silicon, silicon germanium, or a III-V material, for example.

The method 200 may include a second step 220 of surface cleaning. The second step 220 may include a cleaning of a wafer with a cleaning agent. The effect of the second step 220 may be to remove any oxides or native oxides on the surface of the substrate. The presence of oxides or native oxides may degrade performance as it will adversely affect the contact resistivity of the substrate device.

In the second step 220, for example, a germanium silicon wafer may be cleaned with hydrofluoric acid (HF). Other potential cleaning agents include hydrochloric acid (HCl) or NF₃ plasma, for example. In accordance with at least one embodiment of the invention, the second step 120 may comprise a standard wet clean that may take place in a Horizon module provided by ASM International B.V., for example.

The method 200 may include a third step 230 of a dopant layer ALD. The dopant layer deposited in the third step 230 may include antimony, boron, arsenic, phosphorus, magnesium, carbon, silicon, or sulfur, for example. The third step 230 may take place at a temperature ranging between 20° C. and 450° C. The third step 230 may be repeated until a desired thickness is achieved, such as 0.1 nm to 15 nm.

In accordance with at least one embodiment of the invention, a deposition of antimony may take place in the reaction chamber during the third step 230. The temperature of the reaction chamber during the third step 230 may range between 60-120° C., preferably between 60-100° C., and more preferably between 60-80° C. The third step 230 may be repeated as needed in order to obtain a desired thickness for the antimony layer, which in some instances may be 0.5 nm and 10 nm in other instances.

In order to deposit antimony, the third step 230 may include the pulsing of a first precursor comprising a metal halide, such as SbCl₃, SbF₃, SbBr₃, or SbI₃, for example. The pulsing of the first precursor may range in duration between 0.1 and 5 seconds, and preferably between 0.5 and 2 seconds. The third step 230 may then include purging of the first precursor with a purge gas, such as N₂, Ar, or other inert gas. The pulsing of purge gas may range in duration between 5 and 15 seconds, and preferably between 5 and 10 seconds.

In order to deposit antimony, the third step 230 may include the pulsing of a second precursor comprising antimony. The second precursor may comprise at least one of: trimethyl silyl antimony, triethyl silyl antimony, antimony alkoxides, or antimony amides, for example. The second precursor may also comprise antimony bound to silicon atoms having a general formula of Sb(AR¹R²R³)₃, where A is Si or Ge and R¹, R², and R³ are alkyl groups comprising one or more carbon atoms. The pulsing of the second precursor may range in duration between 0.1 and 5 seconds, and preferably between 0.5 and 2 seconds. The third step 230 may then include purging of the second precursor with a purge gas, such as N₂, Ar, or other inert gas. The pulsing of purge gas may range in duration between 5 and 15 seconds, and preferably between 5 and 10 seconds.

The method 200 may include a fourth step 240 of a capping layer ALD. The capping layer deposited may comprise a metal. The metal deposited in the fourth step 240 may include titanium, titanium nitride (TiN), titanium silicide (TiSi_(x)), tantalum silicide (TaSi_(x)), or niobium silicide (NbSi_(x)), for example. The fourth step 240 may include the pulsing of a first precursor comprising a metal halide, such as titanium chloride (TiCl_(x)), tantalum fluoride (TaF_(x)), niobium fluoride (NbF_(x)), or other metal halide, for example. Depending on the capping layer, the timing of pulses may differ. For example, in order to form a silicide, the pulsing of the first precursor may range in duration between 0.01 and 5 seconds, or preferably between 0.5 and 1 second. To form a nitride, the pulsing of the precursor may range in duration between 0.01 and 20 seconds, or preferably between 1 and 15 seconds. The fourth step 240 may include the pulsing of a purge gas, such as N₂, Ar, or other inert gas. The pulsing of purge gas may range in duration between 5 and 30 seconds, and preferably between 5 and 10 seconds.

The fourth step 240 may include the pulsing of a second precursor such as ammonia (NH₃) or silane, for example. The pulsing of the second precursor may range in duration between 0.01 and 30 seconds, or preferably between 1 and 15 seconds. The fourth step 240 may include the pulsing of a purge gas, such as N₂, Ar, or other inert gas. The pulsing of purge gas may range in duration between 5 and 30 seconds, and preferably between 5 and 10 seconds.

The fourth step 240 may take place at a temperature ranging between 20° C. and 600° C., preferably between 200 and 500° C., and more preferably between 300 and 400° C. The fourth step 240 may be repeated until a desired thickness of the capping layer is achieved, such as 0.1 nm to 5 nm, preferably between 0.1 to 3 nm or 0.1 to 2 nm. The thickness of the capping layer may be less than approximately 5 nm, less than approximately 3 nm, less than approximately 2 nm, or preferably less than approximately 1.5 nm.

The method 200 may include a fifth step 250 of a drive-in anneal. During this step, the substrate may be subjected to temperatures at temperature range between 450° C. and 1100° C., resulting in improved dopant drive-in. The annealing may have a duration ranging between 1 second and 30 minutes.

FIG. 3A illustrates a device in accordance with at least one embodiment of the invention. The formed device may comprise a capping layer 310, a dopant layer 320, and a substrate 330. At this point, a capping layer 310 has been deposited, but each of the layers is distinct and separate. In addition, a drive-in anneal has not yet taken place. The dopant layer 320 may comprise antimony, while the substrate 330 may comprise germanium.

FIG. 3B illustrates a device in accordance with at least one embodiment of the invention after a drive in-anneal has taken place. The device has a capping layer 310 and the substrate 330, but the dopant has infiltrated a portion of the substrate 330 to form a doped substrate layer 340. For example, if the dopant is antimony and the substrate is germanium, the doped substrate layer 340 would comprise an antimony-doped germanium layer.

FIG. 3C illustrates a device in accordance with at least one embodiment of the invention after a drive in-anneal has taken place. Like the device in FIG. 3B, a drive-in anneal has taken place, but in this case has not resulted in a complete infiltration of the dopant into the substrate 330. The device may comprise the capping layer 310, the substrate 330, and a doped substrate layer 340, but also includes a dopant layer 320 representing dopant that has not infiltrated into the substrate 330.

The particular implementations shown and described are illustrative of the invention and its best mode and are not intended to otherwise limit the scope of the aspects and implementations in any way. Indeed, for the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the system may not be described in detail. Furthermore, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and/or physical couplings between the various elements. Many alternative or additional functional relationship or physical connections may be present in the practical system, and/or may be absent in some embodiments.

It is to be understood that the configurations and/or approaches described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Thus, the various acts illustrated may be performed in the sequence illustrated, in other sequences, or omitted in some cases.

The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems, and configurations, and other features, functions, acts, and/or properties disclosed herein, as well as any and all equivalents thereof. 

We claim:
 1. A method of forming a semiconductor device for source/drain applications comprising: providing a substrate for processing in a reaction chamber, the substrate having a surface and at least one formed source/drain region; performing an atomic layer deposition of a dopant layer on the substrate surface for incorporation of dopant into the at least one formed source/drain region; and performing an atomic layer deposition of a capping layer on the dopant layer; wherein, after the atomic layer deposition of the capping layer, the semiconductor device is subject to a drive-in anneal step to diffuse dopant from the dopant layer into at least one of the formed source/drain regions, producing a doping level near an interface of greater than 1×10²⁰/cm³ with a diffusion depth less than 30 nm, and wherein performing the atomic layer deposition of the dopant layer on the substrate surface for incorporation of dopant into the at least one formed source/drain region comprises: pulsing a first precursor onto the substrate, wherein the first precursor is at least one of: SbCl₃, SbF₃, SbI₃, and SbBr₃; purging the first precursor from the reaction chamber with a purge gas, wherein the purge gas comprises at least one of: N₂, Ar, or an inert gas; pulsing a second precursor onto the substrate, wherein the second precursor is at least one of: trimethyl silyl antimony or triethyl silyl antimony; and purging the second precursor from the reaction chamber with the purge gas.
 2. The method of claim 1, further comprising: removing the capping layer.
 3. The method of claim 1, wherein the substrate comprises at least one of: silicon, germanium, silicon germanium, or a III-V material.
 4. The method of claim 1, wherein the dopant layer comprises at least one of: antimony, boron, arsenic, phosphorus, magnesium, carbon, silicon, or sulfur.
 5. The method of claim 1, wherein the capping layer comprises at least one of: silicon dioxide (SiO₂), titanium nitride (TiN), silicon nitride (SiN), aluminum nitride (AlN), silicon-containing carbon, or aluminum oxide (Al₂O₃).
 6. The method of claim 1, wherein the drive-in anneal is performed at a temperature greater than 400° C.
 7. The method of claim 1, wherein the atomic layer deposition of the dopant layer forms a channel material for an NMOS device.
 8. The method of claim 1, wherein the substrate comprises germanium.
 9. A method of forming a semiconductor device for source/drain applications comprising: providing a substrate for processing in a reaction chamber, the substrate having a surface and a formed source/drain; performing an atomic layer deposition of a dopant layer on the substrate surface for incorporation of dopant into the at least one formed source/drain region, producing a doping level near an interface of greater than 1×10²⁰/cm³ with a diffusion depth less than 30 nm; and performing an atomic layer deposition of a capping layer on the dopant layer, wherein performing the atomic layer deposition of the dopant layer on the substrate surface for incorporation of dopant into the at least one formed source/drain region comprises: pulsing a first precursor onto the substrate, wherein the first precursor is at least one of: SbCl₃, SbF₃, SbI₃, and SbBr₃; purging the first precursor from the reaction chamber with a purge gas, wherein the purge gas comprises at least one of: N₂, Ar, or an inert gas; pulsing a second precursor onto the substrate, wherein the second precursor is at least one of: trimethyl silyl antimony or triethyl silyl antimony; and purging the second precursor from the reaction chamber with the purge gas.
 10. The method of claim 9, wherein the substrate comprises at least one of: silicon, germanium, silicon germanium, or a III-V material.
 11. The method of claim 9, wherein the dopant layer comprises at least one of: antimony, boron, arsenic, phosphorus, magnesium, carbon, silicon, or sulfur.
 12. The method of claim 9, wherein the capping layer comprises at least one of: titanium; titanium nitride (TiN_(x)); titanium silicide (TiSi_(x)); tantalum silicide (TaSi_(x)); or niobium silicide (NbSi_(x)).
 13. The method of claim 9, wherein a drive-in anneal is performed on the substrate at a temperature greater than 400° C.
 14. The method of claim 9, wherein the atomic layer deposition of the dopant layer forms a channel material for an NMOS device.
 15. The method of claim 9, wherein the substrate comprises germanium.
 16. The method of claim 9, wherein performing the atomic layer deposition of the capping layer comprises: pulsing a first precursor onto the substrate, wherein the first precursor is at least one of: TiCl_(x), TaF_(x), NbF_(x), or a metal halide; purging the first precursor from the reaction chamber with a purge gas, wherein the purge gas comprises at least one of: N₂, Ar, or an inert gas; pulsing a second precursor onto the substrate, wherein the second precursor is at least one of: ammonia (NH₃) or silane; and purging the second precursor from the reaction chamber with the purge gas.
 17. The method of claim 9, the method producing a doping level near an interface of approximately 5×10²⁰/cm³.
 18. The method of claim 1, the method producing a doping level near an interface of approximately 5×10²⁰/cm³. 